Isomerization of epoxyalkenes to 2,5-dihydrofurans

ABSTRACT

Disclosed are processes for the isomerization of epoxyalkenes to dihydrofurans by contacting an epoxyalkene with a catalyst comprising a quaternary organic onium iodide compounds, optionally deposited on a non-acidic support and/or in combination with a Lewis acid co-catalyst The catalyst may comprise a supported catalyst, an unsupported catalyst or a solution of the catalytically-active components in an inert, organic solvent.

This application is a continuation of application Ser. No. 08/194,655, filed Feb. 10, 1994 now U.S. Pat. No. 6,213,691, which is a continuation of application Ser. No. 07/746,530, filed Aug. 19, 1991, now abandoned, which is a divisional of application Ser. No. 07/627,668, filed Dec. 14, 1990, now U.S. Pat. No. 5,082,956, which is a continuation-in-part of application Ser. No. 07/490,208, filed Mar. 8, 1990, now abandoned.

This invention pertains to isomerization processes and, more particularly, to processes whereby γ,δ-epoxy-alkenes and γ,δ-epoxycycloalkenes are isomerized to obtain the corresponding 2,5-dihydrofuran compounds. This invention also pertains to novel catalyst systems useful in the described isomerization processes and to methods for the preparation of supported catalyst systems.

Dihydrofurans are reactive heterocyclic species which are useful in a variety of applications, e.g., as intermediates in the production of useful polymers and chemicals. However, the use of dihydrofurans for such purposes has heretofore been restricted due to the non-availability of cost-effective preparative procedures therefor.

In addition, dihydrofurans are readily reduced to produce the corresponding tetrahydrofuran species, which are also useful in a variety of applications, e.g., as polar aprotic reaction solvents, co-solvents, reactive intermediates in the production of useful polymers, copolymers, and the like.

U.S. Pat. Nos. 3,932,468 and 3,996,248 disclose the production of 2,5-dihydrofurans by the rearrangement of substituted or unsubstituted epoxyalkenes with a homogeneous catalyst system comprising hydrogen iodide or hydrogen bromide and a transition metal Lewis acid in an organic solvent. This process suffers from a number of disadvantages including the use of corrosive hydrogen halides, the need for expensive, high-boiling tertiary amide solvents, e.g., N-methyl-2-pyrrolidinone, to dissolve the transition metal Lewis acid. We have found that the process of U.S. Pat. Nos. 3,932,468 and 3,996,248 also results in the unwanted production of up to 15% α,β-unsaturated aldehydes or ketones.

The thermal (i.e., non-catalytic) rearrangement of 3,4-epoxy-1-butene has been studied and shown by Crawford et al in the Canadian Journal of Chemistry, Vol. 54, pages 3364-3376 (1976) to produce a variety of products, including 2,3-dihydrofuran, cis and trans 2-butenal and 3-butenal.

Other reactions of epoxides have been reported. See, for example, U.S. Pat. No. 4,600,800, where epoxides are converted to allylic alcohols by contacting an epoxide in the liquid phase with solid alumina catalysts.

Another example of the rearrangement of epoxides is described in the Journal of Organometallic Chemistry, Vol. 359, pages 255-266 (1989), wherein Sato et al report the formation of α,β-unsaturated aldehydes and ketones by the rhodium (I) catalyzed isomerization of 1,3-diene monoepoxides.

U.S. Pat. No. 4,897,498 describes an efficient process for the preparation of γ,δ-epoxyalkenes by the selective monoepoxidation of dienes. Thus, a process is needed for the conversion of such epoxyalkenes to dihydrofurans in satisfactory selectivity and/or yields wherein the product may be readily recovered from the catalyst and the catalyst reused and used in continuous operation.

In accordance with the present invention, we have discovered a catalytic process for the isomerization of γ,δ-epoxyalkenes to produce dihydrofurans. The process provides high levels of epoxyalkene conversion with high selectivity to the desired dihydrofuran product. Long catalyst lifetimes are realized and the product may be recovered by relatively simple means since the catalyst and reaction mixture are readily separated by such simple techniques as distillation, decantation, filtration, gas stripping methods, gas/liquid flow separation, and the like.

Our invention also provides novel catalyst systems, both supported and unsupported, which are useful, for example, to promote the isomerization of epoxyalkenes to dihydrofurans. Processes for preparing the supported catalyst systems are also provided herein.

In accordance with the present invention, there is provided a process for the isomerization of γ,δ-epoxyalkenes to the corresponding 2,5-dihydrofuran compounds, which process comprises contacting a γ,δ-epoxyalkene or γ,δ-epoxycycloalkene with a catalytic amount of a quaternary organic onium iodide, e.g., a compound consisting of an ammonium, phosphonium or arsonium cation and an iodide anion, under isomerization conditions of temperature and pressure.

The γ,δ-epoxyalkene and γ,δ-epoxycycloalkene reactants may contain from 4 to about 20 carbon atoms, preferably from 4 to about 8 carbon atoms. Examples of the epoxyalkene and epoxycycloalkene reactants include compounds having the structural formula:

wherein each R¹ is independently selected from hydrogen, alkyl of up to about 8 carbon atoms, a carbocyclic or heterocyclic aryl group of about 5 to 10 carbon atoms or halogen or any two R¹ substituents collectively may represent an alkylene group forming a ring, e.g., alkylene containing in the main chain up to about 8 carbon atoms. The preferred epoxyalkene reactants comprise compounds of formula (I) wherein only two of the R¹ substituents individually may represent lower alkyl, e.g., alkyl of up to about 8 carbon atoms, or collectively represent straight or branched chain alkylene of up to about 8 carbon atoms. Exemplary compounds contemplated for use in the practice of the present invention include 3,4-epoxy-3-methyl-1-butene, 2,3-dimethyl-3,4-epoxy-1-butene, 3,4-epoxycyclooctene, 3,4-epoxy-1-butene, 2,5-dimethyl-2,4-hexadiene mono-epoxide, and the like. The epoxyalkene reactant of primary interest is 3,4-epoxy-1-butene.

The 2,5-dihydrofuran compounds obtained in accordance with our novel process have the structural formula:

wherein the R¹ substituents are defined above. Of the compounds which may be obtained in accordance with our invention, the most important is 2,5-dihydrofuran.

The quaternary onium iodide compounds which may be used as the catalyst in our novel process are known compounds and/or may be prepared according to published procedures. See, for example, U.S. Pat. No. 3,992,432 and the references cited therein. Exemplary quaternary organic onium iodide compounds include mono-, di-, tri-, or tetra-substituted quaternary onium iodides, wherein said substituents are selected from hydrogen, alkyl or substituted alkyl groups, cycloalkyl or substituted cycloalkyl groups, carbocyclic aryl or substituted carbocyclic aryl groups, heteroaryl or substituted heteroaryl groups, ferrocenyl, wherein each of said substituents may be bonded to one another to form a cyclic, heterocyclic, polycyclic or poly-heterocyclic structure. When used on a support or as a melt, the onium compounds normally contain at least 6 carbon atoms, preferably at least 12 carbon atoms, and have melting points not greater than about 225° C., preferably not greater than about 200° C.

Examples of the onium iodide catalysts are compounds conforming to the formulas

(R²)₄Y⁺ I⁻,   (III)

I⁻ (R²)₃Y⁺−R³−Y^(+x)(R²)_(2+x) I_(x) ⁻,   (IV)

wherein

each R² independently is selected from hydrogen, alkyl or substituted alkyl moieties having up to about 20 carbon atoms, cycloalkyl or substituted cycloalkyl having about 5 to 20 carbon atoms, or aryl or substituted aryl having about 6 to 20 carbon atoms; or when Y is P, each R² also may be selected from alkoxy of up to about 20 carbon atoms, cycloalkoxy of about 5 to 20 carbon atoms, aryloxy of 6 to 10 carbon atoms or halogen;

two or three R² substituents collectively may represent joined hydrocarbylene groups, e.g. alkylene having 4 to 6 main chain carbon atoms or unsaturated groups such as —CH═CHCH═CHCH═ and lower alkyl substituted alkylene and unsaturated groups, which form a mono- or poly-cyclic ring with the Y atom to which they are bonded;

each R³ is independently selected from hydrocarbylene moieties or substituted hydrocarbylene moieties;

x is 0 or 1, and

Y is N, P or As; provided that the quaternary onium iodide compound contains at least 6 carbon atoms.

The substituted groups and moieties referred to above bear one or more substituents such as groups having the formulas

—OR⁴,

—Si(R⁴)₃ and X

wherein each R⁴ is independently selected from hydrogen or alkyl of up to about 20 carbon atoms and X is halogen. As used herein, the terms “hydrocarbylene moieties” refers to alkylene moieties having up to about 6 carbon atoms, arylene or polyarylene moieties having 6 to 20 carbon atoms.

The preferred onium iodide catalysts are the quaternary ammonium and quaternary phosphonium iodide compounds. Exemplary ammonium compounds include tetrapentylammonium iodide, tetrahexylammonium iodide, tetraoctylammonium iodide, tetradecylammonium iodide, tetradodecylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, monooctylammonium iodide, dioctylammonium iodide, trioctylammonium iodide, N-octylquinuclidinium iodide, N,N′-dimethyl-N,N′-dihexadecylpiperazinium diiodide, dimethyl-hexadecyl-[3-pyrrolidinylpropyl]ammonium iodide, N,N,N,N′,N′,N′-hexa(dodecyl)octane-1,8-diammonium diiodide, N,N,N,N′,N′,N′-hexa(dodecyl)butane-1,4-diammonium diiodide, N-octylpyridinium iodide, and the like.

Exemplary phosphonium compounds include tetra-octylphosphonium iodide, tetrabutylphosphonium iodide, triphenyl(hexyl)phosphonium iodide, triphenyl(octyl)-phosphonium iodide, tribenzyl(octyl)phosphonium iodide, tribenzyl(dodecyl)phosphonium iodide, triphenyl(decyl)-phosphonium iodide, triphenyl(dodecyl)phosphonium iodide, tetrakis(2-methylpropyl)phosphonium iodide, tris(2-methylpropyl)(butyl)phosphonium iodide, triphenyl(3,3-dimethylbutyl)phosphonium iodide, triphenyl(3-methylbutyl)phosphonium iodide, tris(2-methylbutyl)(3-methylbutyl)phosphonium iodide, triphenyl[2-trimethylsilylethyl]phosphonium iodide, tris(p-chlorophenyl)(dodecyl)phosphonium iodide, hexyl-tris(2,4,6-trimethylphenyl)phosphonium iodide, tetradecyltris(2,4,6-trimethylphenyl)phosphonium iodide, dodecyltris(2,4,6-trimethylphenyl)phosphonium iodide, and the like.

Tetra-substituted ammonium and phosphonium iodide compounds containing a total of about 16 to 60 carbon atoms are especially preferred. Such compounds have the formulas

wherein

each R⁵ substituent independently is selected from alkyl of up to about 20 carbon atoms and each R⁶ substituent is independently selected from R⁵, benzyl, phenyl or phenyl substituted with up to 3 substituents selected from lower alkyl (alkyl of up to about 4 carbon atoms) lower alkoxy or halogen; or

two R⁵ substituents collectively may represent alkylene of 4 to 6 carbon atoms including alkylene of 4 to 6 carbon atoms substituted with lower alkyl; provided, as specified above, that the quaternary iodide compounds contain about 16 to 60 carbon atoms.

Another group of preferred ammonium iodide compounds are comprised of N-alkyl-azabicycloalkane and N-alkyl- and N,N′-dialkyl-diazabicycloalkane iodide compounds containing 6 to about 12 ring carbon atoms, e.g., bicyclic compounds having the general formula

wherein R⁵ is defined above and A is the residue of an azabicycloalkane or diazabicycloalkane having 6 to 12 ring carbon atoms (including the 2 carbon atoms in the above general formula), e.g., azabicyclooctane, azabicyclononane, diazabicyclooctane and the like.

The onium iodide compounds described hereinabove may be employed in combination with a Lewis acid to catalyze the isomerization process of our invention. Examples of such optional Lewis acid co-catalysts include the alkali metal halides, zinc halides, magnesium halides, tin (II) halides, tin (IV) halides, titanium (IV) halides, titanium (IV) tetra-lower-alkoxides, zirconium (IV) halides, manganese (II) halides, iron (III) halides, or iron (III) acetylacetonate. Preferably, the Lewis acid co-catalyst is an alkali metal iodide, zinc iodide, zinc chloride, magnesium iodide, tin (II) iodide, tin (IV) iodide, titanium (IV) iodide, titanium (IV) tetramethoxide, titanium (IV) tetraethoxide, titanium (IV) tetraiso-propoxide, zirconium (IV) iodide, manganese (II) iodide, manganese (II) chloride, iron (III) iodide, iron (III) acetylacetonate or a combination thereof. The Lewis acid co-catalysts which are particularly preferred are polarizable iodides, such as, for example, titanium (IV) iodide, zirconium (IV) iodide, and, especially, zinc iodide and tin (II) iodide.

The Lewis acid co-catalyst alternatively may be selected from organotin (IV) and organoantimony (V) compounds such as hydrocarbyltin trihalides, dihydro-carbyltin dihalides, trihydrocarbyltin halides, tetra-hydrocarbyltin compounds and tetrahydrocarbylantimony halides. Examples of such organometallic compounds include compounds having the formula

(R⁷)_(n)—Sn—Hal_((4−n)) and (R⁷)₄—Sb—Hal

wherein

each R⁷ independently is selected from alkyl or substituted alkyl moieties having up to about 20 carbon atoms, cycloalkyl or substituted cycloalkyl having about 5 to 20 carbon atoms, carbocyclic aryl or substituted carbocyclic aryl having about 6 to 20 carbon atoms, or heteroaryl or substituted heteroaryl moieties having about 4 up to 20 carbon atoms;

Hal is a halogen atom such as bromo or, preferably, iodo; and

n is 1, 2, 3 or 4.

Examples of organometallic compounds include dibutyltin diiodide, tributyltin iodide, trioctyltin iodide, triphenyltin iodide, tributyltin bromide, trimethyltin iodide, butyltin triiodide, tetrabutyltin, tetraoctyltin, triphenyltin iodide, tribenzyltin iodide, dimethyltin diiodide, diphenyltin diiodide, triphenyltin bromide and tetraphenylantimony iodide.

The preferred organometallic compounds comprise tin (IV) iodides having the above general formula and a total carbon content of about 3 to 24 carbon atoms wherein

each R⁷ substituent independently is selected from alkyl of up to about 12 carbon atoms, benzyl, phenyl or phenyl substituted with up to 3 substituents selected from lower alkyl, lower alkoxy or halogen;

Hal is iodo; and

n is 2 or 3.

The quaternary organic onium iodide catalyst, or the quaternary organic onium iodide-Lewis acid catalyst system, may be employed in the process provided by this invention in either a supported or unsupported form. The supported catalysts of this invention comprise an essentially non-acidic catalyst support material having one or more quaternary organic onium iodide compounds distributed on the surface thereof as a substantially continuous and uniform film and, optionally, one or more of the Lewis acids described above, e.g., an alkali metal halide, zinc halide, magnesium halide, tin (II) halide, tin (IV) halide, titanium (IV) halide, titanium (IV) lower alkyl alkoxide, organotitanium (IV) halide, zirconium (IV) halide, manganese (II) halide, iron (III) halide, iron (III) acetylacetonate or one of the organotin compounds or organoantimony halides described hereinabove.

The essentially non-acidic support may be in the form of a powder or shaped material having sufficient structural integrity to allow passage of gaseous reactant through a packed or fluidized bed of the supported catalyst under reaction conditions. Preferred support materials employed in the practice of the present invention are materials having a particle size in the range of about 20 up to 200 microns and having a crush strength of at least about two pounds. Support materials having crush strengths of at least ten pounds are especially preferred.

A variety of shapes are suitable for use as the support material employed in the practice of the present invention. For example, pellets, spheres, rings, saddles, extruded cylinders, and the like can be employed, so long as such materials have dimensions and packing characteristics so as to allow for the ready passage of gaseous reactant and product through a packed or fluidized bed of the catalyst under reaction conditions.

Examples of the materials which may be employed as the support include zinc oxide, zinc carbonate, magnesium oxide, silica, alumina, titanium oxide, lanthanum oxide, boron nitride, boron carbide, silicon nitride, silicon carbide, tin oxide, calcium oxide, barium oxide, strontium oxide, zirconium oxide, carbon, boron phosphate, or zirconium phosphate, as well as mixtures of any two or more thereof. The preferred support materials contemplated for use in the practice of the present invention include zinc oxide, zinc carbonate, magnesium oxide, silica, alumina, titanium oxide, boron nitride, silicon nitride, silicon carbide, calcium oxide, barium oxide and carbon as well as mixtures of any two or more thereof. Silica, alumina, titanium oxide and zinc oxide are particularly preferred support materials.

The amount of the quaternary organic onium iodide component of the novel catalyst compositions of this invention can vary substantially depending, for example, on the particular support material and the form, e.g., surface area, thereof, the mode in which the isomerization process is operated, the particular quaternary onium iodide present, the presence or absence of a Lewis acid co-catalyst, etc. The amount of the onium iodide, calculated as weight iodide, typically will be in the range of about 0.1 to 30 weight percent based on the total weight of the catalyst. Preferred loading levels fall in the range of about 0.5 up to 20 weight percent (same basis).

When present, the quantity of Lewis acid component of the catalyst compositions generally is in the range of about 0.01 to 30 weight percent, based on the total weight of the catalyst. The preferred quantity of the inorganic Lewis acid co-catalysts, e.g., titanium (IV) iodide, zirconium (IV) iodide, zinc iodide and tin (II) iodide, is in the range of about 0.02 up to 5.0 weight percent based on the total weight of the catalyst.

Another embodiment of the catalyst compositions provided by our invention comprise a support material having deposited thereon (i) about 0.1 to 30 weight percent of an organic onium iodide and (ii) about 0.01 to 30 weight percent of an organotin (IV) compound or organoantimony (V) halide, based on the total weight of the catalyst composition. These catalyst compositions preferably comprise:

(i) about 0.5 to 20 weight percent of a tetra-substituted ammonium and/or phosphonium iodide compound of formula (VII) and/or (VIII); and

(ii) about 0.02 to 20 weight percent of an organotin iodide containing a total of about 3 to 24 carbon atoms and having the formula

(R⁷)_(n)—Sn—I_((4−n))

 wherein

each R⁷ substituent independently is selected from alkyl of up to about 12 carbon atoms, benzyl, phenyl or phenyl substituted with up to 3 substituents selected from lower alkyl, lower alkoxy or halogen; and

n is 2 or 3; on

(iii) a support material selected from silica, alumina, zinc oxide, titanium oxide, boron nitride and silicon carbide.

The supported catalysts described herein may be prepared by a variety of procedures as will be readily apparent to those skilled in the art. For example, the supported catalysts may be prepared by the steps comprising:

(a) impregnating a suitable support with a solution of one or more quaternary organic onium iodide compound and, optionally, one or more Lewis acids, and thereafter

(b) removing the solvent from the impregnated support.

Solvents contemplated for use in the impregnation step include polar solvents capable of substantially dissolving the quaternary organic onium iodide and the optionally employed Lewis acid. Such solvents include water, lower alcohols such as methanol, ethanol, isopropyl alcohol, and the like. Preferred solvents are those which can be easily removed by standard evaporative techniques once the desired impregnation has been carried out.

The volume of solvent required is 0.5 to 20.0 ml of solvent (plus quaternary organic onium iodide and, optional Lewis acid) per gram of support, the minimum volume of solvent being defined as that volume required to cover the catalyst support. The support and impregnation solution are agitated (typically by rotary tumbling) for 0.2 to 2.0 hrs at slightly elevated temperatures, e.g., 20 to 60° C., to maximize interaction of support and catalytic components. The solvent is preferentially removed by rotary evaporation at reduced pressure at temperatures ranging from 40 to 100° C., or alternatively by drying in a heated forced air oven, or further alternatively by spray-drying the catalyst solution on the support. After drying, the catalyst is ready to be loaded into a reactor.

Prior to contacting the catalyst with an epoxyalkene under isomerization conditions, the catalyst optionally may be subjected to pre-treatment conditions of time and temperature sufficient to activate said catalyst relative to non-pretreated catalyst. Typical pre-treatment conditions of time and temperature comprise a temperature at least as high as the melting point of said quaternary organic onium iodide, but no greater than 225° C., for a time in the range of about 0.1 up to 10 hours.

The conditions of temperature and pressure and the space velocity employed in our novel isomerization process can vary considerably depending on various factors such as the activity of the catalyst used, the degree of conversion and/or selectivity desired, the gas hour space velocity employed, the mode of operation and the like. For example, the process may be carried out at a temperature in the range of about 60 to 225° C. although temperatures of about 100 to 200° C. are more typical. The total reaction pressure may be in the range of about 1.02 to 70 bar (absolute) with the preferred range being about 1.1 to 20 bar total pressure.

The gas hourly space velocity may be varied substantially, e.g., from about 1 to about 10,000, although our process normally is performed using gas hourly space velocities in the range of about 10 up to 5,000 (hr⁻¹). The epoxyalkene reactant may constitute up to 100% of the feed composition or may be fed along with an inert diluent wherein volume ratio of the epoxyalkene:inert diluent can vary over a wide range of values, typically within 1:100 to 4:1. Exemplary inert gas diluents include helium, argon, nitrogen, carbon dioxide, or hydrocarbons which are gaseous under reaction conditions. Preferably, the epoxyalkene concentration is in the range of about 5 up to 80 volume percent of the feed composition.

The isomerization process may be carried out using the catalysts described herein either in a supported or unsupported form. Thus, the supported catalysts may be utilized in fixed or fluidized beds using reactor configurations well-known to those skilled in the art.

When the catalyst is unsupported, it can be used at temperatures either below, at or above the melting point of the quaternary organic onium iodide salt. When the catalyst is at or above its melting point and exists as a substantially liquid phase, it is necessary to maintain the catalyst in a reactor volume such that the passage of the gaseous feed and product molecules is not restricted, yet contains the catalyst in the reactor volume. An up-flow reactor is suitable for this purpose since the gaseous feed maintains the catalyst in the appropriate position in the reactor, yet permits the passage of unreacted feed and reaction products through the liquid, or substantially liquid, phase catalyst and into the downstream refining/recycle apparatus. In an especially preferred mode of operation, the catalyst is in a vessel with a closed bottom and the feed is added through a gas dispersion apparatus below the level of the catalyst. The unreacted feed and reaction products can exit from the top of the reactor.

The unsupported catalyst system preferably is used in our process as a melt of an intimate mixture of one or more of the quaternary onium iodide compounds and, optionally, one or more of the Lewis acid co-catalysts described hereinabove. The onium iodide:co-catalyst weight ratio of the unsupported catalyst system can vary substantially, e.g. from 500:1 to 1:100, depending on the particular co-catalyst selected. The preferred onium iodide:co-catalyst weight ratios depend on whether the co-catalyst is (1) an organotin (IV) compound or an organoantimony (V) halide or (2) one of the other Lewis acids described herein above. Thus, for the unsupported catalyst systems containing an inorganic Lewis acid, such as titanium (IV) iodide, zirconium (IV) iodide, zinc iodide and tin (II) iodide, the preferred onium iodide:co-catalyst weight ratio is about 200:1 to 5:1 and for the organotin (IV) compounds and organoantimony (V) halides the preferred onium iodide:co-catalyst weight ratio is about 1:100 to 50:1. Particularly preferred unsupported catalyst systems comprise a mixture of one or more of the tetra-substituted ammonium or phosphonium iodide compounds described hereinabove and tin (II) iodide, zinc iodide or an organotin iodide.

The unsupported quaternary organic onium iodide and/or Lewis acid catalyst may be used with an inert organic solvent if desired to alter the reaction conditions and/or reactor configuration. The optional, inert organic solvent may be used, for example, to change the concentration of the quaternary organic onium iodide and/or the Lewis acid or to assist in heat and/or mass transfer characteristics of the catalytic process.

Thus, another embodiment of our invention comprises the isomerization of an epoxyalkene to the corresponding 2,5-dihydrofuran in the presence of a homogeneous catalyst solution. This embodiment may be carried out in the presence of one or more of the above-described organometallic compounds although reaction rates are relatively slow if an organic onium iodide is not included. Accordingly, the homogeneous catalyst solution preferably comprises a catalytic amount of (i) one or more of the above-described organometallic compounds and (ii) one or more of the above-described organic onium iodides in (iii) an inert organic solvent, i.e., a solvent which does not react with the γ,δ-epoxyalkene or γ,δ-epoxycycloalkene reactants or the 2,5-dihydrofuran products. Examples of the solvents which may be used include aliphatic and aromatic hydrocarbons such as heptane, toluene, specific or mixed xylenes, pseudocumene, and mesitylene; halogenated hydrocarbons such as chlorobenzene, 1,2-dichlorobenzene, and 1,1,2,2-tetrachloroethane; ketones such as cyclohexanone, 5-methyl-2-hexanone, and 2-heptanone; ethers such as 2,5-dihydrofuran, tetrahydrofuran, and bis(2-methoxyethyl)ether; esters such as isobutyl acetate; and tertiary amides such as N-methyl-2-pyrrolidinone, N-cyclohexyl-2-pyrrolidinone, N-ethyl-2-pyrrolidinone, and N,N-dimethylacetamide. Normally, for ease of separation, the solvent or mixture of solvents employed have boiling points at least 20° C. above the boiling point of the 2,5-dihydrofuran product and the unsaturated aldehyde or ketone by-products.

The concentrations of the organometallic compound and the optional onium iodide in the inert, organic solvent can be varied substantially depending, for example, on the particular catalytically-effective components present, the design of the reactor system, etc. Typically, the concentration of the organometallic compound will be about 1 to 50 weight percent and the concentration of the onium iodide compound, when present, will be about 1 to 70 weight percent, both concentrations being based on the total weight of the catalyst solution. Normally, the mole ratio of onium iodide to organometallic compound is at least 1:1.

The preferred catalyst solutions comprise

(i) about 1 to 25 weight percent of an organotin iodide containing about a total of about 3 to 24 carbon atoms and having the formula

(R⁷)_(n)—Sn—I_((4−n))

 wherein

each R⁷ substituent independently is selected from alkyl of up to about 8 carbon atoms, benzyl, phenyl or phenyl substituted with up to 3 substituents selected from lower alkyl, lower alkoxy or halogen; and

n is 1, 2, 3 or 4; and

(ii) about 1 to 25 weight percent of a tetra-substituted ammonium or phosphonium iodide of formula (VII) and/or (VIII); and

(iii) an inert organic solvent selected from hydrocarbons and chlorinated hydrocarbons having up to about 10 carbon atoms.

Toluene, mixed or specific xylene isomers, chlorobenzene, mixed or specific dichlorobenzene isomers, pseudocumene, and mesitylene are particularly preferred solvents.

The isomerization process may be carried out in the liquid phase using the catalyst solutions described hereinabove by contacting a γ,δ-epoxyalkene or γ,δ-epoxycycloalkene at a temperature of about 50 to 200° C., preferably about 100 to 150° C., depending on the solvent or mixture of solvents employed. The process may be carried out at atmospheric or super-atmospheric pressures, e.g., up to about 22 bar (absolute).

The process employing the catalyst solution may be carried out in a batch, semi-continuous or continuous mode of operation. For example, batch operation may comprise refluxing a mixture of the γ,δ-epoxyalkene and catalysts, e.g. tributyltin iodide and tetraheptylammonium iodide, in a solvent such as p-xylene for a time sufficient to convert essentially all the epoxide to the 2,5-dihydrofuran. The products are then separated by distillation from the mixture. The undistilled catalyst solution may be reused in a subsequent reaction.

The catalyst solution preferably is employed in a continuous mode of operation wherein a γ,δ-epoxyalkene or γ,δ-epoxycycloalkene is added to a recirculated catalyst solution which is then introduced into a continuous reactor. After isomerization, the reaction stream is fed to a distillation system for removal of product or products and recycle of the catalyst solution. Examples of continuous reactor designs in which the process can be performed are continuous stirred tank reactors and plug flow reactors.

Our novel isomerization process and the catalyst systems, compositions and solutions useful in practicing the process are further illustrated by the following examples.

Preparation of Catalysts EXAMPLE 1

Tetrabutylammonium iodide (1.786 g) was dissolved at 25° C. in ethyl alcohol (80 mL) in a 250 mL, round-bottom flask. Zinc oxide (5.0 g, ultrapure) powder was added and the mixture was agitated for twenty minutes at 40° C. on a rotary evaporator. The zinc oxide used had a surface area of 3.8 square meters per g (m²/g) and a particle diameter in the range of 75 to 150 microns. The alcohol was then removed on the rotary evaporator at 40° C. under vacuum. The supported catalyst obtained contained 18.2 weight percent tetrabutylammonium iodide.

EXAMPLE 2

Tetradodecylammonium iodide (51.24 g), zinc iodide (1.06 g) and ethyl alcohol (200 mL) were placed in a one-liter, fluted flask and placed on a rotary evaporator and agitated for five minutes in a 60° C. bath. Silica extrusions (400 g, Calsicat SiO₂ pellets, {fraction (3/16)}″ diameter having a surface area of approximately 0.5 m²/g and a general composition of 100% SiO₂) were then added and agitation continued for twenty minutes in the bath at 60° C. The alcohol was then removed on the rotary evaporator at 60° C. under vacuum. The supported catalyst obtained contained 11 weight percent tetradodecylammonium iodide and 0.23 weight percent zinc iodide.

EXAMPLE 3

Triphenyl(hexyl)phosphonium iodide (0.250 g) and zinc iodide (0.0050 g) were placed in a 50-mL flask and then silica (2.0 g) was added. The silica support material was prepared by grinding the silica extrudate described in Example 2 and classifying the ground material and using the portion which passed a 10 mesh sieve and was retained on a 20 mesh. The flask was placed on a rotary evaporator and agitated for 20 minutes with the flask in the bath at 60° C. Methanol was removed while the flask was in the 60° C. bath using vacuum. The supported catalyst obtained (2.25 g) contained 11 weight percent triphenyl(hexyl)phosphonium iodide and 0.11 weight percent zinc iodide.

The catalyst compositions set forth in the examples of Table I were prepared using the procedures described in the preceding examples. The Weight Percent given in Table I refers to the weight percent of the quaternary onium iodide present based on the total weight of the catalyst. The zinc oxide and silica used as the support materials were the same as the support materials described in Examples 1 and 3.

TABLE I Weight Example Quaternary Onium Iodide Support Percent 4 Tetrapropylammonium iodide ZnO 15.8 5 Tetrabutylammonium iodide ZnO 22 6 Tetrapentylammonium iodide ZnO 20.4 7 Tetrahexylammonium iodide ZnO 22.5 8 Tetraoctylammonium iodide ZnO 26.0 9 Tetradecylammonium iodide ZnO 18.0 10 Tetradodecylammonium iodide ZnO 21.0 11 Trioctylammonium iodide ZnO 21.0 12 Dioctylammonium iodide ZnO 18.0 13 Octylammonium iodide ZnO 13.0 14 N,N′-Dimethyl-N,N′-hexa- ZnO 20.0 decylpiperizinium diiodide 15 N,N-Dimethyl-N-hexadecyl-N- ZnO 19.0 [3-pyrrolidinonopropyl]- ammonium iodide 16 N,N,N,N′,N′,N′-hexa-(dodecyl)- ZnO 30.0 octane-1,4-diammonium diiodide 17 N,N,N,N′,N′,N′-hexa-(dodecyl)- ZnO 29.0 butane-1,4-diammonium diiodide 18 N-Octylpyridinium iodide ZnO 16.0 19 Tetraoctylphosphonium iodide SiO₂ 11.0 20 Tetrabutylphosphonium iodide SiO₂ 11.0 21 Tetradodecylammonium iodide SiO₂ 11.0

The catalysts set forth in Table II were prepared from a quaternary onium iodide compound, a Lewis acid co-catalyst and a support material according to the procedures described in Examples 1-3. The Weight Percent given for each example refers to the weight of the co-catalyst present on the supported catalyst based on the total weight of the catalyst. The materials described in Examples 1 and 3 were used as the catalyst supports. The onium iodide compound and the weight percent thereof present on each catalyst and the support material of each of the Table II examples were:

Examples 22-32: 11% Tetradodecylammonium iodide on SiO₂

Examples 33-42: 26% Tetraoctylammonium iodide on ZnO

Examples 43-48: 11% Tetraoctylphosphonium iodide on SiO₂

Examples 49-51: 11% Tetrabutylphosphonium iodide on SiO₂

TABLE II Weight Example Co-catalyst Percent 22 ZnI₂ 0.22 23 ZnCl₂ 0.22 24 SnI₂ 0.27 25 SnI₂ 0.54 26 SnI₂ 1.10 27 MgI₂ 0.22 28 MnI₂ 0.22 29 ZrI₄ 0.27 30 TiI₄ 0.22 31 Titanium tetra- 0.22 isopropoxide 32 Iron (III) acetyl- 0.11 acetonate 33 ZnI₂ 1.7 34 SnI₂ 2.2 35 SnI₄ 1.8 36 LiI 1.5 37 ZnI₂ 0.9 38 ZnI₂ 3.4 39 ZnI₂ 8.5 40 SnI₂ 0.27 41 SnI₂ 0.54 42 SnI₂ 1.1 43 ZnI₂ 0.055 44 ZnI₂ 0.11 45 ZnI₂ 0.15 46 ZnI₂ 0.23 47 ZnI₂ 0.55 48 SnI₂ 0.11 49 ZnI₂ 0.11 50 ZnI₂ 0.55 51 ZnI₂ 2.3

The supported catalysts described in Example 52-57 were prepared by procedures analogous to Example 3 using the silica support material described in Example 3, zinc iodide and the quaternary ammonium iodide compound given in each example. Each catalyst contained 11 weight percent of the quaternary ammonium iodide compound and 0.11 weight percent zinc iodide, based on the total weight of the catalyst.

EXAMPLE 52 N-Hexyl-1,4-diazabicyclo[2.2.2]octane iodide EXAMPLE 53 N-Tetradecyl-1,4-diazabicyclo[2.2.2]octane iodide EXAMPLE 54 N-Hexyl-1,4-diazabicyclo[2.2.2]octane iodide hydroiodide EXAMPLE 55 N-Octylazabicyclo[2.2.2]octane iodide EXAMPLE 56 N-Methyl-N-dodecylpyrrolidinium iodide EXAMPLE 57 Tetrakis-(3-methylbutyl)ammonium iodide

The supported catalysts described in Example 58-71 were prepared by procedures analogous to and using the silica support material described in Example 3, zinc iodide and the quaternary phosphonium iodide compound given in each example. Each catalyst contained 11 weight percent of the quaternary phosphonium iodide compound and 0.11 (Examples 58 and 60) or 0.055 (Examples 59 and 61-72) weight percent zinc iodide, based on the total weight of the catalyst.

EXAMPLE 58 Tribenzyl(octyl)phosphonium iodide EXAMPLE 59 Triphenyl(hexyl)phosphonium iodide EXAMPLE 60 Tribenzyl(dodecyl)phosphonium iodide EXAMPLE 61 Triphenyl(octyl)phosphonium iodide EXAMPLE 62 Triphenyl(decyl)phosphonium iodide EXAMPLE 63 Triphenyl(dodecyl)phosphonium iodide EXAMPLE 64 Tris(2-methylpropyl)(butyl)phosphonium iodide EXAMPLE 65 Tris(2-methylpropyl)(3-methylbutyl)phosphonium iodide EXAMPLE 66 Tris(3-chlorophenyl)(dodecyl)phosphonium iodide EXAMPLE 67 Triphenyl(3-methylbutyl)phosphonium iodide EXAMPLE 68 Triphenyl(trimethylsilylmethyl)phosphonium iodide EXAMPLE 69 Tris(2,4,6-trimethylphenyl)(hexyl)phosphonium iodide EXAMPLE 70 Tris(2,4,6-trimethylphenyl)(dodecyl)phosphonium iodide EXAMPLE 71 Tris(2,4,6-trimethylphenyl)(tetradecyl)phosphonium iodide EXAMPLE 72 Tetrakis(2-methylpropyl)phosphonium iodide EXAMPLE 73

Silica support material described in Example 3 was contacted with tetraoctylphosphonium iodide, tetradodecylammonium iodide and zinc iodide to obtain a supported catalyst bearing 5.5 weight percent tetraoctylphosphonium iodide, 5.5 weight percent tetradodecylammonium iodide and 0.22 weight percent zinc iodide.

Examples 74-83 describe supported catalysts prepared from a quaternary ammonium compound and a variety of support materials. The percent given in each of the examples refers to the weight percent of the quaternary ammonium compound specified on the support based on the total weight of the catalyst. The catalysts of Examples 78-83 also contained 0.23 weight percent zinc iodide.

EXAMPLE 74

26% Tetraoctylammonium iodide on silicon nitride powder having a surface area of 11.9 m²/g and a mean particle size of 60 microns.

EXAMPLE 75

26% Tetraoctylammonium iodide on boron nitride powder having a surface area of 2.9 m²/g, a bulk density of 2.1 g/cm3 and a particle diameter in the range of 50-100 microns.

EXAMPLE 76

22% Tetrabutylammonium iodide on zinc carbonate powder having a particle diameter in the range of 75-150 microns.

EXAMPLE 77

22% Tetrabutylammonium iodide on magnesium oxide powder having a surface area of 1.0 m²/g and a particle diameter in the range of 75-150 microns.

EXAMPLE 78

11% Tetradodecylammonium iodide on alumina (Calsicat SE) spheres: ⅛″ diameter spheres with a surface area of 10 m²/g, a total pore volume=0.44 cc (Hg)/g, packing density of 0.81 g/cm³, crush strength=18 lbs, and a general composition by weight percent of: Al₂O₃=99.7, SiO₂=0.1, Na₂O=0.1 and Fe₂O₃=0.08.

EXAMPLE 79

11% Tetradodecylammonium iodide on alumina (Norton 5552) rings: ¼″ rings having a surface area of 0.43 m²/g, a total pore volume of 0.37 cc (Hg)/gm, a median pore diameter of 7μ, a packing density of 0.80 g/cm³, and a chemical composition by weight percent of: Al₂O₃=93.1, SiO₂=5.6, Fe₂O₃=0.3, TiO₂0.1, CaO=0.1, MgO=0.3, Na₂O=0.1, K₂O=0.1.

EXAMPLE 80

11% Tetradodecylammonium iodide on alumina (Norton 08228) pellets: {fraction (3/16)}″ diameter pellets with a surface area of 0.25 m²/g, a total pore volume of 0.23 cc (Hg)/gm, a median pore diameter of 19μ, a packing density of 0.90 g/cm³, and a chemical composition by weight percent of: Al₂O₃=84.7, SiO₂=13.4, Fe₂O₃=0.21, TiO₂=0.47, CaO=0.21, MgO=0.12, Na₂O=0.15, K₂O=0.26.

EXAMPLE 81

11% Tetradodecylammonium iodide on zinc oxide (Calsicat ZnO) extrudate: ⅛″ diameter extrudate with a surface area of 3.0 m²/g, a packing density of 1.5 g/cm³, a crush strength of 11 pounds, and a nominal chemical composition of 100% ZnO.

EXAMPLE 82

18% Tetradecylammonium iodide on alumina (Norton 82326) spheres: {fraction (3/16)}″ diameter spheres having a surface area of 0.39 m²/g, a total pore volume of 0.36 cc(Hg)/g, a median pore diameter of 5.4 microns, a packing density of 0.94 g/cm³, and a chemical composition by weight percent of: Al₂O₃=93.1, SiO₂=5.6, Fe₂O₃=0.3, MgO=0.3, TiO₂=0.1 and Na₂O=0.1.

EXAMPLE 83

18% Tetradecylammonium iodide on titanium dioxide (Degussa) extrudate: {fraction (1/16)}″ diameter extrudate having a surface area of 50 m²/g and a chemical composition by weight percent of: TiO₂=99.5, Al₂O₃=0.3, and SiO₂=0.2.

The following examples illustrate the preparation of the catalyst compositions comprising an organic onium iodide and an organotin halide on a catalyst support material.

EXAMPLE 84

Triphenyl(hexyl)phosphonium iodide (0.75 g) and triphenyltin iodide (0.0151 g) were placed in a 50 mL flask and dissolved in 30 mL of anhydrous methanol at 30° C. To this solution was added 6.0 g of silica support. The silica support material was prepared by grinding silica pellets 0.1875 inch in diameter and classifying the ground material and using the portion which passed a 10 mesh sieve and was retained on a 20 mesh. The flask was placed on a rotary evaporator and agitated for 20 minutes with the flask in the bath at 50° C. Methanol was removed while the flask was in the 60° C. bath using vacuum. The supported catalyst obtained (6.75 g) contained 11 weight percent triphenyl(hexyl)phosphonium iodide and 0.22 weight percent triphenyltin iodide.

EXAMPLE 85

A supported catalyst consisting of 11 weight 15 percent tetradodecylammonium iodide and 0.22 weight percent tributyltin iodide on silica was prepared according to the general procedure described in Example 84.

EXAMPLE 86

A supported catalyst consisting of 11 weight percent tetradodecylammonium iodide and 1.1 weight percent triphenyltin iodide on silica was prepared according to the general procedure described in Example 84.

Isomerization of Epoxybutenes

The supported catalysts described hereinabove were used to isomerize 3,4-epoxy-1-butene under steady state conditions in a 1 atmosphere, single-pass flow reactor system. The reactor tube was constructed of Pyrex glass and the catalyst charge (between 0.1 and 20.0 g) was held in place by means of a Pyrex glass frit. The geometries of the reactor and catalyst particles as well as bed depth were chosen to maintain and measure the true kinetic and catalytic aspects of the reaction. Gas hourly space velocities (GHSV, mL gas fed per hour per mL catalyst) for all experiments fell within the range of about 30 up to 3000. A chromel/alumel thermocouple sheathed in stainless steel was embedded within the catalyst bed to measure the true reaction temperature.

The 3,4-epoxy-1-butene reactant was added by flowing helium through a liquid-vapor saturator containing the liquid reactant. The reactant was maintained at constant temperature by coupling the saturator to a refrigerated constant temperature circulator bath which was capable of maintaining the temperature-of the liquid-vapor saturator at ±1° C. accuracy from −10° C. to +120° C. The helium flow used to sweep the 3,4-epoxy-1-butene vapor from the saturator to the reactor inlet was maintained using a mass flow controller over the range 2-100 mL (standard temperature and pressure) per minute. The feed compositions fed to the reactor consisted of from 0.01 to 0.33 bar 3,4-epoxy-1-butene pressure (absolute) with the balance He to give a total pressure of approximately 1 to 1.5 bar at GHSV ranging from 30 to 3000. Reaction product analyses (as well as feed composition analyses) were made using an in-line gas sampling loop connected directly to the inlet of a Varian 3760 gas chromatograph. The reaction products were analyzed using a packed Chromosorb 101 column (8 feet by 2 mm interior diameter Pyrex glass capillary column) connected to a flame ionization detector.

Further, by means of a switching valve, it was possible to divert the feed stream through the in-line sample loop prior to passage over the catalyst. In this way, quantitative analysis of the feed stream and comparison to the corresponding data from the reactor effluent were possible, thereby providing very accurate measurements of both conversion levels and product selectivities. Output from the flame ionization (FI) detector was integrated using a computing integrator which was programmed to give both absolute quantities and rates of formation. All reactor exit lines were heated and maintained at 125-140° C. to prevent product condensation.

The GC analysis was performed using the following temperature programming schedule: an initial temperature of 100° C. was held for 2 minutes, followed by a temperature program rate of +10° C. per minute up to a final temperature of 200° C. which was held for 7 minutes. The helium GC carrier rate was 20 mL per minute.

The catalyst and conditions employed and the results obtained in each of the isomerization experiments are set forth in Tables III and IV wherein Temp is the temperature in °C. at which the reaction occurred, Press is the 3,4-epoxy-1-butene partial pressure in bars absolute of the gas fed, GHSV is defined above, Conv is the mole percent of moles 3,4-epoxy-1-butene converted to other compounds per moles of 3,4-epoxy-1-butene fed and Select is the mole percent of 3,4-epoxy-1-butene converted to 2,5-dihydrofuran based on the moles of 3,4-epoxy-1-butene converted.

EXAMPLE 87-114

These examples demonstrate the use of supported catalysts bearing only a quaternary onium iodide as the catalytic component. In Examples 87-96 and Examples 99-101 the catalysts were subjected to a pretreatment at elevated temperatures in an inert atmosphere for 30-60 minutes prior to starting the reactant feed. The pretreatments were performed at 140° C. except in Examples 87 and 88 wherein temperatures of 160° C. and 150° C., respectively, were used.

TABLE III Catalyst Example of Example Temp Press GHSV Conv Select 87 4 130 0.03 240 6 21 88 1 140 0.03 240 48 68 89 5 140 0.03 240 49 68 90 5 160 0.03 240 52 63 91 6 140 0.03 240 28 78 92 7 140 0.03 240 17 83 93 8 130 0.03 240 41 94 94 8 125 0.03 540 9 91 95 8 130 0.03 540 13 94 96 8 140 0.03 540 26 95 97 9 130 0.03 240 58 90 98 10 130 0.03 240 78 94 99 11 130 0.03 240 79 69 100 12 130 0.03 300 73 40 101 13 130 0.03 300 67 61 102 14 130 0.03 300 5 31 103 14 170 0.03 300 82 58 104 15 130 0.03 300 2 3 105 15 167 0.03 300 55 65 106 16 130 0.03 300 49 94 107 16 130 0.09 300 32 91 108 17 130 0.03 300 97 90 109 17 130 0.03 600 93 90 110 18 130 0.03 240 72 80 111 19 120 0.03 300 1 19 112 19 130 0.03 300 2 31 113 19 140 0.03 300 2 41 114 20 160 0.03 300 0.4 54

EXAMPLES 115-250

These examples demonstrate the favorable effect of using a Lewis acid co-catalyst in conjunction with a quaternary onium iodide compound as evidenced by an increase in the conversion of the 3,4-epoxy-1-butene reactant and/or increasing the selectivity to the desired 2,5-dihydrofuran. In Examples 137-140 the catalysts were subjected to a pretreatment in flowing helium at 140° C. for 30-60 minutes prior to starting the reactant feed.

TABLE IV Catalyst Example of Example Temp Press GHSV Conv Select 115 2 125 0.17 75 64 91 116 2 125 0.17 190 38 94 117 2 130 0.17 75 83 93 118 2 130 0.17 190 50 93 119 2 130 0.17 750 14 92 120 21 120 0.09 300 0.2 36 121 21 130 0.09 300 0.3 45 122 21 140 0.09 300 0.6 67 123 22 130 0.09 300 28 93 124 23 130 0.09 300 15 87 125 24 120 0.09 300 5 99 126 24 130 0.09 300 7 99 127 24 140 0.09 300 8 98 128 25 120 0.09 300 7 94 129 25 130 0.09 300 12 93 130 26 120 0.09 300 10 96 131 27 130 0.09 300 6 75 132 28 130 0.09 300 8 93 133 29 130 0.09 300 15 98 134 30 130 0.09 300 2 95 135 31 130 0.09 300 6 71 136 32 130 0.09 300 8 95 137 33 130 0.03 300 86 90 138 34 130 0.03 300 84 85 139 35 130 0.03 300 56 72 140 36 130 0.03 300 73 85 141 37 130 0.03 300 62 89 142 38 130 0.03 300 90 82 143 39 130 0.03 300 92 62 144 40 120 0.09 300 7 99 145 40 140 0.09 300 8 98 146 41 120 0.09 300 13 94 147 42 120 0.09 300 10 96 148 42 130 0.09 300 15 65 149 43 130 0.09 300 12 97 150 44 130 0.09 300 16 95 151 44 130 0.13 300 15 95 152 45 120 0.09 60 79 98 153 45 120 0.09 240 35 95 154 46 120 0.09 300 30 97 155 46 130 0.09 300 32 96 156 46 140 0.09 300 37 94 157 47 120 0.09 300 55 85 158 48 120 0.09 300 7 93 159 48 130 0.09 300 11 94 160 49 120 0.09 300 18 97 161 49 130 0.09 300 23 96 162 50 120 0.09 300 54 85 163 51 125 0.03 300 92 80 164 51 135 0.03 300 93 75 165 51 150 0.03 300 96 68 166 52 140 0.09 300 10 85 167 52 150 0.09 300 16 85 168 52 160 0.09 300 23 83 169 53 140 0.09 300 6 91 170 53 150 0.09 300 12 88 171 53 160 0.09 300 26 86 172 53 170 0.09 300 44 80 173 53 180 0.09 300 56 75 174 54 131 0.09 300 18 80 175 54 141 0.09 300 27 82 176 55 130 0.09 300 9 88 177 55 140 0.09 300 11 90 178 55 160 0.09 300 13 82 179 56 120 0.09 300 10 75 180 57 120 0.09 300 10 88 181 57 130 0.09 300 13 87 182 57 140 0.09 300 18 87 183 57 160 0.09 300 34 88 184 3 130 0.09 300 17 85 185 3 140 0.09 300 27 86 186 3 150 0.09 300 42 88 187 3 160 0.09 300 50 86 188 3 170 0.09 300 57 85 189 58 120 0.09 300 18 93 190 58 130 0.09 300 26 94 191 58 140 0.09 300 30 94 192 58 150 0.09 300 43 93 193 59 130 0.09 60 38 89 194 59 140 0.09 60 84 89 195 59 140 0.09 120 60 91 196 60 130 0.09 300 35 95 197 60 160 0.09 300 55 92 198 61 140 0.09 300 26 90 199 61 160 0.09 300 41 90 200 62 140 0.09 300 30 92 201 62 160 0.09 300 45 90 202 63 130 0.09 300 37 94 203 64 130 0.09 300 27 90 204 65 140 0.09 300 24 92 205 66 140 0.09 300 26 79 206 67 130 0.09 300 9 61 207 67 170 0.09 300 15 75 208 68 140 0.09 300 11 62 209 69 160 0.09 300 12 71 210 69 180 0.09 300 68 95 211 70 160 0.09 300 64 93 212 71 140 0.09 300 34 95 213 71 160 0.09 300 50 94 214 72 140 0.09 300 12 80 215 72 160 0.09 300 28 85 216 73 125 0.09 300 21 95 217 73 130 0.09 300 37 94 218 74 130 0.03 540 5 81 219 74 150 0.03 540 20 80 220 75 130 0.09 540 3 80 221 75 130 0.03 540 7 80 222 75 160 0.03 540 29 73 223 76 140 0.03 240 15 50 224 76 160 0.03 240 50 49 225 77 140 0.03 540 10 35 226 77 160 0.03 540 15 41 227 77 170 0.03 240 59 61 228 78 125 0.17 150 65 51 229 79 125 0.09 75 55 86 230 79 125 0.09 190 29 84 231 80 125 0.17 90 68 93 232 80 125 0.17 250 34 92 233 80 125 0.17 500 16 93 234 80 125 0.17 1000 8 93 235 80 130 0.17 1000 18 93 236 81 125 0.17 250 8 78 237 81 130 0.17 250 13 85 238 82 130 0.03 60 11 64 239 82 135 0.03 60 25 77 240 82 140 0.03 60 48 83 241 83 130 0.03 160 32 63 242 83 135 0.03 160 36 64 243 83 140 0.03 160 53 67 244 84 150 0.09 600 8 81 245 84 160 0.09 600 10 78 246 85 130 0.09 300 14 98 247 85 130 0.09 600 8 98 248 85 140 0.09 300 22 98 249 86 130 0.09 300 13 99 250 86 140 0.09 300 26 98

EXAMPLE 251-255

Using the catalyst of Example 2 and the isomerization procedure described hereinabove, two other γ,δ-epoxyalkenes and a γ,δ-epoxycycloalkene were isomerized to 2,5-dihydrofuran compounds. The reactants used and the desired dihydrofuran product obtained were:

Example Reactant Dihydrofuran Product 251, 252 2-Methyl-3,4-epoxy- 3-methyl-2,5-dihydro- 1-butene furan 253, 254 2,3-Dimethyl-3,4- 3,4-Dimethyl-2,5-di- epoxy-1-butene dihydrofuran 255 3,4-epoxycyclo- 9-oxa-bicyclo[4.2.1]- octene non-7-ene

The results obtained are set forth in Table V wherein Conv is the mole percent of moles of reactant converted to other products per moles of reactant fed and Select is the percent moles of reactant converted to the desired 2,5-dihydrofuran product based on the moles of reactant converted.

TABLE V Example Temp Press GHSV Conv Select 251 126 0.04 60 65 66 252 126 0.04 120 46 67 253 127 0.03 60 51 81 254 127 0.05 60 46 81 255 130 0.01 60 61 90

EXAMPLE 256-300

These examples demonstrate the use of the unsupported catalyst systems of this invention in the isomerization of 3,4-epoxy-1-butene to 2,5-dihydrofuran according to the general procedure described relative to the preceding isomerization examples. Because the catalyst can exist in a substantially molten state if the process is operated above the melting point of the quaternary onium iodide salt, the reactor was operated in an upward flow mode whereby the gaseous feed entered below the catalyst bed and passed through a gas dispersion frit upon which the unsupported catalyst system was supported to maintain the catalyst in the proper position in the reactor. Alternatively, the catalyst was maintained in a vessel with a closed bottom into which the feed gas was added below the level of the substantially molten catyalyst by means of a gas dispersion apparatus. In both reactor configurations, the gaseous reactor effluent comprising unreacted feed and product exited the top of the reactor into the downstream assembly described hereinabove.

In the examples utilizing an unsupported catalyst system, the catalyst components were heated in an inert gas flow, typically 100 mL (STP) per minute of helium, until both catalyst components existed in a molten state. At this point, a partial pressure of 3,4-epoxy-1-butene was introduced into the carrier gas stream and the catalytic reaction was initiated. Typical molar concentrations of 3,4-epoxy-1-butene in the carrier gas varied from 3 to 25%, with 9 to 10% being the most commonly used feed concentration.

The unsupported catalyst systems listed below were prepared by physically and intimately mixing the components while in the solid state and were used in Examples 256-326. For catalyst components which were potentially air sensitive, care was taken to prevent contact with air while loading into the catalytic reactor.

(i) Tetradodecylammonium iodide (1.20 g) and zinc iodide (24.0 mg)

(ii) Triphenyl(hexyl)phosphonium iodide (1.00 g) and zinc iodide (5.0 mg)

(iii) Triphenyl(hexyl)phosphonium iodide (0.50 g), tris-(2,4,6-trimethylphenyl)(hexyl)phosphonium iodide (0.50 g) and zinc iodide (5.0 mg)

(iv) Tetradodecylammonium iodide (20.0 g) and tributyltin iodide (0.52 g)

(v) Tetradodecylammonium iodide (10.0 g) and dibutyltin diiodide (0.30 g)

(vi) Tetradodecylammonium iodide (10.0 g) and triphenyltin iodide (0.29 g)

(vii) Triphenyl(hexyl)phosphonium iodide (10.0 g) and tributyltin iodide (0.07 g)

(viii) Triphenyl(hexyl)phosphonium iodide (10.0 g) and dibutyltin diiodide (0.21 g)

(ix) Tetradodecylammonium iodide (10.0 g) and trioctyltin iodide (0.36 g)

(x) Triphenyl(hexyl)phosphonium iodide (10.0 g) and trioctyltin iodide (0.25 g)

(xi) Tetrabutylarsonium iodide (8.00 g) and trioctyltin iodide (0.54 g)

(xii) Tetraoctylarsonium iodide (8.00 g) and trioctyltin iodide (0.38 g)

(xiii) Triphenyl(hexyl)phosphonium iodide (11.6 g) and triphenyltin iodide (0.24 g)

(xiv) Triphenyl(hexyl)phosphonium iodide (11.6 g) and triphenyltin iodide (0.59 g)

(xv) Triphenyl(hexyl)phosphonium iodide (11.6 g) and triphenyltin iodide (2.33 g)

(xvi) Triphenyl(hexyl)phosphonium iodide (6.0 g) and triphenyltin iodide (6.0 g)

(xvii) Triphenyl(hexyl)phosphonium iodide (2.0 g) and triphenyltin iodide (10.0 g)

(xviii)Triphenyl(hexyl)phosphonium iodide (0.60 g) and triphenyltin iodide (11.4 g)

(xix) Triphenyl(hexyl)phosphonium iodide (0.10 g) and triphenyltin iodide (10.0 g)

(xx) Triphenyl(hexyl)phosphonium iodide (2.0 g) and tricyclohexyltin iodide (10.4 g)

(xxi) Triphenyl(hexyl)phosphonium iodide (2.0 g) and tribenzyltin iodide (10.9 g)

The ratio of zinc iodide to quaternary onium iodide compound(s) in each of catalyst systems (i) and (ii) is the same as the analogous ratio for the supported catalysts of Examples 22 and 59, respectively.

TABLE VI Catalyst Example System Temp Press GHSV Conv Select 256 (i) 110 0.09 500 17 77 257 (i) 120 0.09 500 44 90 258 (i) 130 0.09 500 60 93 259 (i) 140 0.09 500 88 94 260 (ii) 140 0.09 1200 25 91 261 (ii) 150 0.09 1200 30 90 262 (ii) 160 0.09 1200 36 87 263 (ii) 160 0.09 2400 18 91 264 (iii) 130 0.09 600 17 82 265 (iii) 140 0.09 600 43 92 266 (iii) 160 0.09 600 59 86 267 (iii) 180 0.09 600 72 80 268 (iv) 130 0.09 120 95 95 269 (iv) 130 0.09 300 75 98 270 (iv) 130 0.09 600 60 99 271 (v) 130 0.09 240 96 96 272 (v) 130 0.09 600 83 97 273 (v) 130 0.09 1200 34 96 274 (vi) 130 0.09 240 98 98 275 (vi) 130 0.09 600 78 99 276 (vi) 130 0.09 1200 55 99 277 (vi) 140 0.09 240 98 95 278 (vi) 140 0.09 600 89 98 279 (vi) 140 0.09 1200 75 98 280 (vii) 140 0.09 120 68 81 281 (vii) 140 0.09 600 24 88 282 (viii) 130 0.09 240 71 93 283 (viii) 130 0.09 600 37 94 284 (viii) 130 0.09 1200 21 94 285 (viii) 140 0.09 240 80 90 286 (viii) 140 0.09 1200 22 92 287 (ix) 130 0.09 600 40 99 288 (ix) 130 0.09 1200 20 98 289 (ix) 140 0.09 600 68 98 290 (ix) 140 0.09 1200 46 99 291 (ix) 140 0.09 240 89 96 292 (x) 130 0.09 300 53 90 293 (x) 130 0.09 600 30 92 294 (x) 130 0.09 1200 14 94 295 (x) 140 0.09 600 43 91 296 (x) 140 0.09 1200 20 93 297 (xi) 130 0.09 300 80 97 298 (xi) 130 0.09 600 65 98 299 (xii) 130 0.09 300 28 98 300 (xii) 130 0.09 600 18 98 301 (xiii) 130 0.10 300 38 93 302 (xiii) 130 0.10 600 22 94 303 (xiv) 130 0.10 300 80 93 304 (xiv) 130 0.10 600 67 93 305 (xiv) 140 0.10 300 88 92 306 (xiv) 140 0.10 600 74 92 307 (xv) 130 0.10 300 87 95 308 (xv) 130 0.10 600 69 95 309 (xv) 140 0.10 300 91 95 310 (xv) 140 0.10 600 71 94 311 (xv) 140 0.25 600 64 95 312 (xvi) 130 0.10 300 100 97 313 (xvi) 130 0.10 600 99 97 314 (xvii) 130 0.10 300 100 98 315 (xvii) 130 0.10 600 100 98 316 (xvii) 130 0.25 300 99 97 317 (xvii) 130 0.25 1000 91 97 318 (xviii) 130 0.10 300 80 97 319 (xviii) 130 0.10 600 67 97 320 (xviii) 130 0.25 600 62 97 321 (xix) 130 0.10 300 68 96 322 (xix) 130 0.10 600 56 96 323 (xx) 130 0.10 300 14 96 324 (xx) 130 0.10 600 9 96 325 (xxi) 130 0.10 300 70 85 326 (xxi) 130 0.10 600 54 81

EXAMPLES 327-331

The following examples illustrate the isomerization of 3,4-epoxy-1-butene to 2,5-dihydrofuran using the catalyst solutions described hereinabove. The gas chromatographic (GC) analyses were performed on a Hewlett-Packard 5890A gas chromatograph with a DB5-30W capillary column; temperature program 35° C. (4.5 minutes), 20° C./minute to 260° C. (hold 6 minutes). 1H NMR analyses were performed on a Varian Gemini 300 spectrometer (300 MHz) using CDCl3 as solvent and tetramethylsilane as internal standard.

EXAMPLE 327

To a nitrogen-purged, 500-mL, four-neck flask equipped with a thermometer, addition funnel, condenser, magnetic stirrer, and heating mantle was charged 170.57 g of p-xylene, 21.62 g (0.05185 moles) of tributyltin iodide, and 39.76 g (0.07394 moles) of tetraheptylammonium iodide. The mixture was heated to 109° C. and 34.04 g (0.4857 moles) of 3,4-epoxy-1-butene was added dropwise over 15 minutes at 109-117° C. Thirty minutes after the addition the reaction was complete as shown by GC. After cooling, the condenser was replaced with a fractional distillation apparatus and the mixture distilled. A 36.81 g fraction boiling at 62-134° C. was collected which had the following GC assay: 0.11% furan, 0.32% 3,4-epoxy-1-butene, 1.32% crotonaldehyde, 88.86% 2.5-dihydrofuran, and 9.39% p-xylene. The yield of 2,5-dihydrofuran was 96.1%.

EXAMPLE 328

To a nitrogen-purged, 500-mL, four-neck flask equipped with a thermometer, addition funnel, condenser, magnetic stirrer, and heating mantle was charged 213.58 g of p-xylene, 28.81 g (0.06910 moles) of tributyltin iodide, and 32.27 g (0.05785 moles) of dodecyltri-phenylphosphonium iodide. The mixture was heated to 110° C. and 34.66 g (0.4945 moles) of 3,4-epoxy-1-butene was added dropwise over 18 minutes at 110-119° C. Thirty-five minutes after the addition the reaction was complete as shown by GC. After cooling, the condenser was replaced with a fractional distillation apparatus and the mixture distilled. A 35.22 g fraction boiling at 59-105° C. was collected which had the following GC assay: 0.2% 3,4-epoxy-1-butene, 0.4% crotonaldehyde, 87.2% 2.5-dihydrofuran, and 8.6% p-xylene. The yield of 2,5-dihydrofuran was 87.2%.

EXAMPLE 329

The process of this invention may be operated continuously as shown by this example. The continuous reaction system consists of a heated, plug-flow reactor (465 mL, U-tube of Pyrex glass) into which the 3,4-epoxy-1-butene and recirculated catalyst solution is pumped. After a residence time in the reactor at the rearrangement temperature the homogeneous reaction stream feeds into the center of a fractional distillation column. The volatile materials are condensed with a water-cooled condenser and collected in the receiver. The stripped catalyst solution from the distillation pot is returned to the reactor along with fresh 3,4-epoxy-1-butene. This system was charged with a solution of 41.7 g (0.100 mole) of tributyltin iodide, 47.4 g (0.123 mole) of tetrabutylphosphonium iodide, and 525 mL of o-dichlorobenzene. The reactor tube was heated to 130° C. and the distillation pot was heated to reflux (pot temperature 205-213° C.). The catalyst solution was recycled at a rate of 30.2 mL/minute and 3,4-epoxy-1-butene was fed at a rate of 1.2 g/minute giving a total flow rate through the reactor of 32 mL/minute for a reactor residence time of 15 minutes. A total of 400.2 g (5.710 mole) of 3,4-epoxy-1-butene was fed to the system and 371.5 g of distillate (bp 66° C.) was obtained. The distillate had a GC analysis of 92.7% 2,5-dihydrofuran, 2.95% of 3,4-epoxy-1-butene, and 0.48% of crotonaldehyde. The assay yield of 2,5-dihydrofuran was 86.1%.

EXAMPLE 330

To a nitrogen-purged, 100-mL, three-neck flask equipped with a thermometer, condenser, magnetic stirrer, and heating mantle was charged 50 mL of p-xylene, 4.35 g (0.0104 moles) of tributyltin iodide, 6.49 g (0.0121 moles) of tetraheptylammonium iodide and 10.28 g (0.1222 moles) of 3,4-epoxy-3-methyl-1-butene. The mixture was heated to reflux (119° C.). After two hours the reaction was complete as judged by GC. After cooling, the condenser was replaced with a distillation head and the mixture distilled. A 17.26 g fraction boiling at 82-120° C. was collected which had the following NMR weight-percent assay: 70.3% p-xylene, 24.3% 3-methyl-2,5-dihydrofuran, and 5.5% 2-methyl-2-butenal. The yield of 3-methyl-2,5-dihydrofuran was 40.8% and the yield of 2-methyl-2-butenal was 9.2%.

EXAMPLE 331

To a nitrogen-purged, 25-mL, three-neck flask equipped with a thermometer, condenser, magnetic stirrer, and heating mantle was charged 12.5 mL of p-xylene, 0.94 g (0.023 moles) of tributyltin iodide, 1.69 g (0.00314 moles) of tetraheptylammonium iodide and 3.10 g (0.0235 moles) of 3,4-epoxycyclooctene (94.1%). The mixture was heated to reflux (125° C.). After five hours the reaction was complete as shown by GC. After cooling, the tetraheptylammonium iodide solids were filtered then the filtrate was filtered through a small pad of silica gel and rinsed with p-xylene. The solvent was distilled off at atmospheric pressure leaving 2.43 g of an oil which had the following NMR weight-percent assay: 42.8% 9-oxabicyclo[4.2.1]non-7-ene and 57.2% p-xylene. The yield of 9-oxabicyclo[4.2.1]non-7-ene was 35.7%.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. 

I claim:
 1. A process for the isomerization of a γ,δ-epoxyalkene or a γ,δ-epoxycycloalkene to the corresponding 2,5-dihydrofuran which comprises contacting a γ,δ-epoxyalkene or a γ,δ-epoxycycloalkene with a catalytic amount of a quaternary organic onium iodide compound and a Lewis acid selected from organotin (IV) and organoantimony (V) compounds.
 2. The process according to claim 1, wherein the γ,δ-epoxyalkene is 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, or 3,4-epoxy-2-methyl-1-butene.
 3. The process according to claim 2, wherein the onium iodide compound is a phosphonium iodide compound having the formula

where each R⁶ substituent is independently selected from alkyl of up to 20 carbon atoms, benzyl, phenyl, and phenyl substituted with up to 3 substituents selected from lower alkyl, lower alkoxy, and halogen, and the phosphonium iodide compound contains about 16 to 60 carbon atoms.
 4. The process according to claim 3, wherein the phosphonium iodide compound is trioctyl(octadecyl)phosphonium iodide, tridodecyl(hexyl)phosphonium iodide, tridodecyl(butyl)phosphonium iodide, trioctyl(hexadecyl)phosphonium iodide, tetra(decyl)phosphonium iodide, or tetradodecylphosphonium iodide.
 5. The process according to claim 1, wherein the onium iodide compound is an ammonium iodide compound having the formula

where each R⁵ substituent is independently selected from alkyl of up to 20 carbon atoms, two R⁵ substituents collectively may represent alkylene of 4 to 6 carbon atoms or alkylene of 4 to 6 carbon atoms substituted with lower alkyl and the quaternary ammonium iodide contains about 16 to 60 carbon atoms.
 6. The process according to claim 5, wherein the ammonium iodide compound is tetradodecylammonium iodide, tetra(decyl)ammonium iodide, tetraoctylammonium iodide, tetraheptylammonium iodide, tetraheptylammonium iodide, or tetrabutylammonium iodide.
 7. The process according to claim 1, wherein the onium iodide compound comprises a mixture of tetra-substituted ammonium or phosphonium iodide compounds.
 8. The process according to claim 1, wherein the Lewis acid is dibutyltin diiodide, tributyltin iodide, trioctyltin iodide, triphenyltin iodide, tributyltin bromide, trimethyltin iodide, butyltin triiodide, tribenzyltin iodide, dimethyltin diiodide, diphenyltin diiodide, triphenyltin bromide, or tetraphenylantimony iodide.
 9. The process according to claim 1, which is carried out in the absence of an inert organic solvent. 